NH3 hybrid reforming as a co-feed stream for high pressure NH3 reforming and hydrocarbon / CO2 reforming

Abstract

The present invention relates to a particular method for reforming ammonia, the method comprising the steps of: (i) providing a reactor containing a catalyst comprising a metal M1 selected from the group consisting of Ni, Co, or Ni and Co; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into the reactor prepared in (i) and contacting the feed gas stream with a catalyst, the contacting being at a pressure of 1 to 50 bara and a temperature of 400 to 1,100° C.; (iv) withdrawing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2. Includes.

Description

[Technical field]

[0001] The present invention relates to a method for reforming ammonia, and more particularly to a method for reforming ammonia and hydrocarbons. [Background technology]

[0002] NH3 is considered as the energy vector of the future, capable of storing large amounts of H2 chemically. Therefore, there is the potential for large-scale production of sustainable NH3 from renewable energy sources. On-site reforming of NH3 (see Equation 1 below) where HH2 is needed could be the final step to close the H2 value chain based on renewable electricity.

[0003] For example, Teramoto et al., Int. J. of Hydr. and Energ., 2020, 45, 8965-8974, relates to the use of a combined NH3 and CH4 feed stream as part of a solid oxide fuel cell concept, while Lu et al., Int. J. of Hydr. and Energ., 2014, 39, 35, 19990-19999, reports on the production of hydrogen by dry reforming of CH4 or NH3 using an electric arc reactor for plasma generation.

[0004] WO 2021 / 175785 A1 relates to a steam purification step to extract amines and NH3 prior to the reforming step.

[0005] WO 2013 / 068905A and WO 2013 / 118078A relate to Ni and Co catalysts for the reforming of hydrocarbons with or without CO2, respectively.

[0006] Top. Catal. (2016) 59: 1438-1457 discusses the use of Ni and Co based catalysts in NH3 reforming, and the process described therein is carried out at low pressures below 10 bara. For NH3 reforming at high pressures above 10 bara, Catal. Sci. Technol., 2020, 10, 5027-5035 discloses the use of Ru based catalysts. Summary of the Invention [Problem to be solved by the invention]

[0007] To obtain H2 directly at high pressures (10-50 bara), the NH3 reforming itself must also be carried out at these pressures. Therefore, there is still a need for improved, cost-efficient NH3 reforming processes that allow to directly supply H2 at the conditions required for further reactions. [Means for solving the problem]

[0008] Thus, surprisingly, a process has been found that uses Ni and Co based catalysts that are active and very stable at high temperatures (>500° C.) for NH3 reforming processes that approach equilibrium conversion at high temperatures and pressures.

[0009] Traditionally, reforming processes (see equations (1)-(5) below: steam reforming is equation 2, dry reforming is equation 3, and their mixture is equation 4; autothermal reforming processes are not described) are used to produce synthesis gas with a specific stoichiometric coefficient (R=(H2-CO2) / (CO2+CO)). Steam reforming gives R values ​​>2, dry reforming gives R values ​​<2. Reforming under dry conditions (unspecified stoichiometry; see equation 4), where a certain amount of H2O is added as steam to the CO2 and hydrocarbons, gives an R value between steam and dry reforming (see equations 2 and 3). Reforming under dry conditions aims to achieve a low steam to carbon ratio, for example to avoid coke formation and maximize process efficiency.

[0010] Each process using syngas requires a dedicated R-value. For example, in methanol synthesis, R-values ​​of 2.0 to 2.3 are often applied. For example, within the concept of carbon capture and utilization (CCU), dry reforming and reforming under dry conditions are processes where large amounts of CO2 are used. If CH4 (representative of a hydrocarbon) is for example of biogenic origin, a sustainable syngas is formed.

[0011] Unexpectedly, it was found that some catalysts that work very well under the reforming conditions described in equations (2)-(4) are also capable of NH3 reforming. Surprisingly, the combined reforming of NH3 as a co-feed stream to the reforming of hydrocarbons with or without CO2 was found, since the reforming of NH3 directly supplies the H2 required to adjust the R value to a specific value. Equation (5) shows an exemplary application of the combined reforming process, here in a stoichiometrically unspecified manner, ideally using one and the same reactor. TIFF2024546870000001.tif34161

[0012] Thus, in summary, the endothermic NH3 reforming (equation 1) is carried out in a wide pressure range (1-50 bara), in particular at high pressure (10-50 bara) and high temperature (400-1100 °C, in particular 500-980 °C) to obtain H2 as part of a sustainable H2 value chain. Corresponding processes and catalysts have been developed. As the reforming processes (e.g. CH4 / CO2 / H2O) follow the same temperature and pressure conditions and the catalysts based on Ni and Co are identical, further processes are provided that combine the reforming process of NH3 with, for example, the reforming of hydrocarbons / CO2 / H2O (see equation 5 as a whole).

[0013] It was therefore an object of the present invention to provide an improved catalytic process capable of reforming NH3 to form H2, carried out in a wide pressure range (1-50 bara), in particular at high pressure (10-50 bara). NH3 reforming is applied as the sole reaction / feed stream or in combination with the reforming of hydrocarbons. When combined reforming is applied, NH3 is supplied as a co-feed stream to a gas mixture, e.g. for reforming under dry conditions containing hydrocarbons, CO2, and H2O.

[0014] Ni-based catalysts utilized for NH3 reforming have already been identified as being active at relatively low temperatures below 400° C. Other catalysts have been identified that are active at higher temperatures above 450° C. Unexpectedly, it was found that the high-temperature active catalysts are also suitable for the combined NH3 and hydrocarbon reforming approach.

[0015] Thus, Co and Ni based catalysts have been identified that can be utilized for hydrocarbon reforming and, surprisingly, also perform very well in NH3 reforming, serving as an enabler for a hybrid reforming approach where the same catalyst can produce syngas with R-values ​​that match those of the corresponding downstream applications (e.g. MeOH production, DME production, or Fischer-Tropsch processes).

[0016] Thus, quite unexpectedly, it has been found that these catalysts can utilize NH3 in any configuration for NH3 reforming alone or as a co-feed stream for the reforming of hydrocarbons with or without CO2 with any amount of NH3 feed.

[0017] For example, the idea of ​​CO2 hydrogenation to form methanol in a carbon capture and utilization (CCU) concept relies heavily on the supply of hydrogen. Typically, hydrogen is provided by H2O electrolysis. For a sustainable and environmentally friendly methanol concept, electricity for the electrolysis needs to be generated in a renewable manner. The drawback of renewable power sources is their non-stationarity (wind or solar). As a result of the fluctuating power sources, the electrolysis and downstream utilization, e.g. methanol synthesis, also have to be operated dynamically (specific on-off scenarios). An approach combining the CO2 methanolization technology with, e.g., NH3 and hydrocarbon (e.g., CH4) / CO2 hybrid reforming under dry conditions, as described in this application, could potentially provide more H2 when the electrolysis supply is low. This is easily achieved by increasing the NH3 co-feed in the hybrid reforming approach. This concept is in principle applicable to any synthesis gas-related process, including H2O electrolysis combined with hybrid reforming as described in this application.

[0018] The present invention therefore provides a method for reforming ammonia, comprising the steps of: (i) providing a reactor containing a catalyst comprising a metal M1 selected from the group consisting of Ni, Co, or Ni and Co; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into the reactor prepared in (i) and contacting the feed gas stream with a catalyst, the contacting being at a pressure of 1 to 50 bara and a temperature of 400 to 1,100° C.; (iv) withdrawing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2. The present invention relates to a method comprising the steps of: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The contact is preferably carried out at a pressure in the range of 5 to 50 bara, more preferably 10 to 50 bara, more preferably 15 to 45 bara, more preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 28 bara, more preferably 20 to 25 bara.

[0020] The contact is preferably carried out at a temperature in the range of 450 to 1000°C, more preferably 475 to 975°C, more preferably 500 to 900°C, more preferably 550 to 800°C, more preferably 600 to 750°C, more preferably 650 to 700°C.

[0021] The feed gas stream prepared in (ii) preferably comprises 1-100 vol.% NH3, more preferably 3-99.99 vol.%, more preferably 5-99.95 vol.%, more preferably 10-99.9 vol.%, more preferably 12-99.9 vol.%, more preferably 20-99.8 vol.%, more preferably 22-99.8 vol.%, more preferably 30-99.7 vol.%, more preferably 40-99.6 vol.%, more preferably 50-99.5 vol.%.

[0022] The feed gas stream prepared in (ii) preferably comprises 0-50 vol.% N2, more preferably 0.01-30 vol.%, more preferably 0.02-25 vol.%, more preferably 0.03-15 vol.%, more preferably 0.04-10 vol.%, more preferably 0.05-5 vol.%, more preferably 0.1-1 vol.%, more preferably 0.12-0.5 vol.%, more preferably 0.14-0.16 vol.%.

[0023] The feed gas stream prepared in (ii) preferably comprises 0-75 vol.% H, more preferably 0-60 vol.%, more preferably 0-50 vol.%, more preferably 0-40 vol.%, more preferably 0-35 vol.%, more preferably 0-30 vol.% H.

[0024] It is preferred that the feed gas stream prepared in (ii) contains 200-20,000 ppmv, more preferably 500-15,000 ppmv, more preferably 800-10,000 ppmv, more preferably 1,000-5,000 ppmv HO.

[0025] The total amount of NH3, N2, and H2 contained in the feed gas stream prepared in (ii) is preferably in the range of 90 to 100 wt%, more preferably 95 to 99.95 vol%, more preferably 98 to 99.9 vol%, more preferably 99 to 99.85 vol%, more preferably 99.7 to 99.8 vol%.

[0026] Preferably, the process is for the reforming of ammonia and hydrocarbons, and the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and the effluent gas stream withdrawn in (iv) further comprises CO.

[0027] When the process is for reforming ammonia and hydrocarbons, and the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and H2O, and the effluent gas stream extracted in (iv) further comprises CO, it is preferred that the feed gas stream prepared in (ii) further comprises CO2 and one or more hydrocarbons, more preferably the feed gas stream comprises 5 vol.% or less of H2O, more preferably 3 vol.% or less, more preferably 1 vol.% or less, more preferably 0.5 vol.% or less, more preferably 0.1 vol.% or less, more preferably 0.05 vol.% or less, more preferably 0.01 vol.% or less of H2O. Furthermore, independently therefrom, it is preferred that the feed gas stream prepared in (ii) further comprises H2O and one or more hydrocarbons, more preferably the feed gas stream comprises 5 vol.% or less of CO2, more preferably 3 vol.% or less, more preferably 1 vol.% or less, more preferably 0.5 vol.% or less, more preferably 0.1 vol.% or less, more preferably 0.05 vol.% or less, more preferably 0.01 vol.% or less of CO2. Additionally, independently, it is preferred that the feed gas stream prepared in (ii) further comprises CO2, H2O, and one or more hydrocarbons.

[0028] When the process is for reforming of ammonia and hydrocarbons, it is further preferred that the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, more preferably C1-C10 alkanes and mixtures thereof, more preferably C3-C9 alkanes and mixtures thereof, more preferably C4-C8 alkanes and mixtures thereof, more preferably C5-C7 alkanes and mixtures thereof, more preferably C6 alkanes and mixtures thereof. Furthermore, independently, it is preferred that the contacting is carried out at a pressure in the range of 10-50 bara, more preferably 12-45 bara, more preferably 15-40 bara, more preferably 18-35 bara, more preferably 20-30 bara. Furthermore, independently, it is preferred that the feed gas stream prepared in (ii) comprises 0.1-75 vol.%, more preferably 0.3-60 vol.%, more preferably 0.5-50 vol.%, more preferably 0.8-40 vol.%, more preferably 1-30 vol.%, more preferably 12-25 vol.% NH3. Further, independently, it is preferred that the feed gas stream prepared in (ii) comprises 10-70 vol%, more preferably 12-60 vol%, more preferably 15-50 vol%, more preferably 20-40 vol%, more preferably 22-29 vol% of one or more hydrocarbons. Further, independently, it is preferred that the feed gas stream prepared in (ii) comprises 0-75 vol%, more preferably 0.5-70 vol%, more preferably 1-68 vol%, more preferably 3-66 vol%, more preferably 5-64 vol%, more preferably 8-62 vol%, more preferably 10-60 vol%, more preferably 25-50 vol%, more preferably 33-44 vol% of HO. Further independently, it is preferred that the feed gas stream prepared in (ii) comprises 0-60% by volume CO2, more preferably 1-58% by volume, more preferably 3-56% by volume, more preferably 5-54% by volume, more preferably 8-52% by volume, more preferably 10-50% by volume, more preferably 12-20% by volume.Additionally and independently, it is preferred that the feed stream exhibits a HO:C molar ratio, which is HO to carbon contained in the one or more hydrocarbons, in the range of from 0 to 4, more preferably from 0.1 to 3, more preferably from 0.1 to 3, more preferably from 0.3 to 2.5, more preferably from 0.4 to 2, more preferably from 0.5 to 1.6.

[0029] When the H2O:C molar ratio, H2O to carbon in the one or more hydrocarbons, is in the range of 0 to 4, it is preferred that the catalyst comprises Ni and that the feed stream exhibits a H2O:C molar ratio, H2O to carbon in the one or more hydrocarbons, in the range of 0.6 to 3, more preferably 0.7 to 2.5, more preferably 0.8 to 2, more preferably 0.9 to 1.6. Independently therefrom, it is preferred that the catalyst comprises Co and that the feed stream exhibits a H2O:C molar ratio, H2O to carbon in the one or more hydrocarbons, in the range of 0.2 to 2.5, more preferably 0.3 to 2, more preferably 0.4 to 1.8, more preferably 0.5 to 1.5.

[0030] When the process is for the reforming of ammonia and hydrocarbons, it is further preferred that the feed stream exhibits a CO2:C molar ratio, CO2 to carbon in the one or more hydrocarbons, in the range of 0 to 4, more preferably 0.1 to 3, more preferably 0.2 to 2, more preferably 0.3 to 1.5, more preferably 0.4 to 0.8. Furthermore, independently thereto, it is preferred that the feed stream exhibits a NH3:C molar ratio, NH3 to carbon in the one or more hydrocarbons, in the range of 0 to 5, more preferably 0 to 4, more preferably 0.001 to 3, more preferably 0.005 to 2, more preferably 0.01 to 1.

[0031] According to the present invention, the feed stream is 500 to 16,000 h -1 , more preferably 700 to 14,000 h -1 , more preferably 800 to 12,000 h -1 , more preferably 900 to 10,000 hours -1 , more preferably 950 to 8,500 hours -1 , more preferably 1,000 to 8,000 hours-1 It is preferred that the gas be fed to the reactor at a gas hourly space velocity in the range of

[0032] When the process is for the reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream withdrawn in (iv) further comprises CO2.

[0033] Furthermore, independently thereto, when the process is for the reforming of ammonia and hydrocarbons, it is further preferred that the effluent gas stream withdrawn in (iv) exhibits a stoichiometric coefficient R in the range of 0.1 to 3, where R is defined according to formula (I):

number

[0034] If the effluent gas stream extracted in (iv) exhibits a stoichiometric coefficient R, it is preferred that R is in the range of 1 to 2.5, more preferably 1.3 to 2.2.

[0035] Additionally, and independently, it is preferred that R>2.

[0036] Independently, the effluent gas stream withdrawn in (iv) preferably exhibits a H2:CO molar ratio of greater than 2.

[0037] If the effluent gas stream extracted in (iv) exhibits a stoichiometric coefficient R, it is preferred that the stoichiometric coefficient R is in the range of 0.5 to 3, more preferably 1 to 2.2, more preferably 1.3 to 1.7.

[0038] When the process is for reforming of ammonia and hydrocarbons, it is further preferred that the effluent gas stream withdrawn in (iv) comprises 10-90% by volume, more preferably 20-80% by volume, more preferably 30-70% by volume, more preferably 40-65% by volume, more preferably 45-60% by volume of H2. Furthermore, independently of that, it is further preferred that the effluent gas stream withdrawn in (iv) comprises 1-70% by volume, more preferably 3-50% by volume, more preferably 5-40% by volume, more preferably 10-35% by volume, more preferably 15-30% by volume of CO2. Furthermore, independently of that, it is further preferred that the effluent gas stream withdrawn in (iv) comprises 1-50% by volume, more preferably 3-45% by volume, more preferably 5-40% by volume, more preferably 8-35% by volume, more preferably 10-30% by volume, more preferably 12-25% by volume of CO2.

[0039] According to the present invention, the effluent gas stream withdrawn in (iv) is preferably used in a process for the production of methanol, a process for the production of dimethyl ether or a process for the production of methanol and dimethyl ether.

[0040] The effluent gas stream withdrawn in (iv) is preferably used in a hydrocarbon production process, more preferably according to a Fischer-Tropsch process.

[0041] The effluent gas stream withdrawn in (iv) is preferably used in a process for the production of an alcohol, more preferably an alkanol, more preferably a C1-C10 alkanol, more preferably a C2-C8 alkanol, more preferably a C2-C6 alkanol, more preferably a C2-C4 alkanol, more preferably a C2 alkanol, more preferably ethanol.

[0042] After (i) and before (iii), it is preferred that the catalyst contained in the reactor provided in (i) is reduced in an atmosphere comprising hydrogen.

[0043] In the case where the catalyst contained in the reactor prepared in (i) is reduced in an atmosphere containing hydrogen after (i) and before (iii), the reduction is preferably carried out at a temperature in the range of 450°C to 980°C, more preferably 500°C to 950°C, more preferably 600°C to 920°C, more preferably 700°C to 890°C, more preferably 750°C to 870°C, more preferably 800°C to 850°C. Furthermore, independently of this, the reduction is preferably carried out in an atmosphere containing 1 to 99% by volume, more preferably 3 to 90% by volume, more preferably 5 to 80% by volume, more preferably 6 to 50% by volume, more preferably 7 to 30% by volume, more preferably 8 to 20% by volume, more preferably 9 to 15% by volume of H2. Furthermore, independently of this, the atmosphere preferably contains 1 to 99% by volume, more preferably 5 to 95% by volume, more preferably 10 to 90% by volume, more preferably 30 to 70% by volume, more preferably 45 to 55% by volume of inert gas. Furthermore, independently, it is preferred that the inert gas comprises one or more gases selected from the group consisting of rare gases and nitrogen gas, more preferably from the group consisting of He, Ar, Ne, and N2, more preferably the inert gas comprises Ar, N2, or Ar and N2, more preferably the inert gas comprises N2, and more preferably the inert gas is N2.

[0044] According to the present invention, in the initial stages of the process, it is preferred that the feed gas stream prepared in (ii) and fed to the reactor in (iii) further comprises H2 for reducing the catalyst.

[0045] In the initial stages of the process, when the feed gas stream prepared in (ii) and fed to the reactor in (iii) further comprises H2 for reducing the catalyst, it is preferred that the feed gas stream further comprises 2-80 vol.%, more preferably 5-70 vol.%, more preferably 10-60 vol.%, more preferably 20-50 vol.%, more preferably 30-40 vol.% H2.

[0046] According to the present invention, it is preferred that the catalyst comprised in the reactor provided in (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe and Ru (including mixtures of two or more thereof), more preferably from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe and Ru (including mixtures of two or more thereof), more preferably from the group consisting of K, Na, Cs, Ba, Mo, Fe and Ru (including mixtures of two or more thereof), more preferably from the group consisting of K, Ba, Mo, Fe and Ru (including mixtures of two or more thereof), more preferably from the group consisting of Fe, Ru or the group consisting of Fe and Fe, preferably M2 comprises Ru, more preferably M2 is Ru.

[0047] The catalyst contained in the reactor provided in (i) preferably further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, the one or more support materials being preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, and mixtures thereof, more preferably the support material comprises Al2O3. Further, independently thereto, it is preferred that the catalyst contained in the reactor prepared in (i) exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, more preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, more preferably 40:60 to 50:50.

[0048] When the catalyst contained in the reactor prepared in (i) exhibits a specific M2:M1 atomic ratio, it is preferred that M2 comprises, and is preferably Fe, and the catalyst exhibits an M2:M1 atomic ratio in the range of 1:99 to 80: more preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, more preferably 40:60 to 50:50. Furthermore, independently thereto, it is preferred that M2 comprises, and is preferably Ru, and the catalyst exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, more preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, more preferably 5:95 to 6:94.

[0049] According to the present invention, it is preferred that the catalyst contained in the reactor prepared in (i) further comprises Al and O.

[0050] When the catalyst contained in the reactor prepared in (i) further comprises Al and O, it is preferred that the catalyst comprises Ni as metal M1, preferably the metal M1 is Ni.

[0051] When the catalyst contained in the reactor prepared in (i) contains Ni as the metal M1, the catalyst preferably further contains Mg, and the molar ratio of Ni:Mg:Al is preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), more preferably 1:(2.0-2.4):(4.0-4.4). Furthermore, independently of that, it is preferable that 95-100% by weight, more preferably 97-100% by weight, more preferably 98-100% by weight, more preferably 99-100% by weight, more preferably 99.5-100% by weight, more preferably 99.9-100% by weight of the catalyst is composed of Ni, Mg, Al, and O. Furthermore, independently of this, it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst consists of M2, Ni, Mg, Al, and O.

[0052] When the catalyst contained in the reactor prepared in (i) further comprises Al and O, it is preferred that the catalyst comprises Co as the metal M1, more preferably the metal M1 is Co.

[0053] When the catalyst contained in the reactor prepared in (i) contains Co as the metal M1, the catalyst preferably further contains La, and the molar ratio of Co:La:Al is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), more preferably 1:(1.3-1.7):(10-12). Furthermore, independently of that, it is preferable that 95-100% by weight, more preferably 97-100% by weight, more preferably 98-100% by weight, more preferably 99-100% by weight, more preferably 99.5-100% by weight, more preferably 99.9-100% by weight of the catalyst is composed of Co, La, Al, and O. Furthermore, independently of this, it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst consists of M2, Co, La, Al, and O.

[0054] The catalyst contained in the reactor provided in (i) is preferably in the form of a compact, more preferably the compact is in the form of a tablet.

[0055] If the catalyst is in tablet form, according to a first option, the tablet form preferably has a four-hole cross section, more preferably a diameter in the range of 12 to 19 mm, more preferably in the range of 16 to 18 mm, more preferably in the range of 16.7 to 16.8 mm, and a height in the range of 7 to 11 mm, more preferably in the range of 9.5 to 10.5 mm, more preferably in the range of 9.7 to 10.0 mm. The tablet form is preferably a calcined tablet form, the calcination being carried out in a gas atmosphere having a temperature more preferably in the range of 350 to 450 ° C, more preferably in the range of 360 to 440 ° C, more preferably in the range of 375 to 425 ° C, more preferably in the range of 390 to 410 ° C, the gas atmosphere more preferably containing oxygen, more preferably this is one or more of oxygen, air or lean air, and the calcination is more preferably carried out for 0.5 to 20 hours, more preferably 1 to 15 hours, more preferably 2 to 10 hours, more preferably 3 to 5 hours. The tablet shape preferably has a lateral crushing strength 1 (SCS1) of at least 70N, more preferably in the range of 70-250N, more preferably in the range of 70-130N, when determined as described in Reference Example 2, where the tablet shape has four cylindrical segments each arranged in the region between two longitudinal grooves, and the lateral crushing strength 1 is measured according to Reference Example 2 under conditions where the tablet shape stands on the two cylindrical segments sandwiching the longitudinal grooves. The tablet shape preferably has a lateral crushing strength 2 (SCS2) of at least 60N, preferably in the range of 60-200N, more preferably in the range of 60-88N, when determined as described in Reference Example 2, where the tablet shape has four cylindrical segments each arranged in the region between two longitudinal grooves, and the lateral crushing strength 2 is measured according to Reference Example 2 under conditions where the tablet shape stands on the cylindrical segments. The tablet shape preferably has a lateral crushing strength 3 (SCS3) of at least 190 N, preferably in the range of 190 to 350 N, more preferably in the range of 190 to 240 N, when determined as described in Reference Example 2, wherein the tablet shape has four cylindrical segments each located in the area between two longitudinal grooves, and the lateral crushing strength 3 is measured according to Reference Example 2 under conditions where the area of ​​the cylindrical segments is perpendicular to the direction of the force applied to the tablet shape.

[0056] Furthermore, when the catalyst is in tablet form, according to the second option, it is preferred that the tablet form has a four-hole cross section, more preferably with a diameter in the range of 10 to 18 mm, more preferably in the range of 13.5 to 16.0 mm, more preferably in the range of 14.0 to 15.5 mm, and a height in the range of 5 to 11 mm, more preferably in the range of 7.5 to 9.4 mm, more preferably in the range of 8.2 to 9.0 mm. It is preferred that the tablet form is a calcined tablet form, and the calcination is carried out in a gas atmosphere having a temperature in the range of 800 to 1400 ° C, more preferably in the range of 875 to 1275 ° C, more preferably in the range of 950 to 1250 ° C, more preferably in the range of 1050 to 1225 ° C, the gas atmosphere more preferably containing oxygen, more preferably this is one or more of oxygen, air, or lean air, and the calcination is carried out for more preferably 0.5 to 20 hours, more preferably 1 to 15 hours, more preferably 2 to 10 hours, more preferably 3 to 5 hours. The tablet shape preferably has a lateral crushing strength 1 (SCS1) of at least 366 N, more preferably at least 400 N, more preferably in the range of 400 to 800 N, more preferably 400 to 600 N, more preferably in the range of 400 to 570 N, when determined as described in Reference Example 1, and the molded body preferably has a tablet shape having a four-hole cross section and four longitudinal grooves, in which four cylindrical segments are each arranged in the region between two longitudinal grooves, and the lateral crushing strength 1 is measured according to Reference Example 1 under conditions in which the tablet shape stands between the two cylindrical segments sandwiching the longitudinal grooves. The tablet shape preferably has a lateral crushing strength 2 (SCS2) of at least 170N, more preferably at least 190N, more preferably in the range of 190-450N, more preferably in the range of 190-300N, more preferably in the range of 190-270N, when determined as described in Reference Example 1, wherein the tablet shape has four cylindrical segments each located in the area between two longitudinal grooves, and the lateral crushing strength 2 is measured according to Reference Example 1 under conditions where the tablet shape stands on its cylindrical segments.The tablet shape preferably has a lateral crushing strength 3 (SCS3) of at least 345 N, more preferably at least 500 N, more preferably in the range of 500 to 950 N, more preferably in the range of 500 to 800 N, more preferably in the range of 500 to 770 N, when determined as described in Reference Example 1, wherein the tablet shape has four cylindrical segments each disposed in an area between two longitudinal grooves, and the lateral crushing strength 3 is preferably measured according to Reference Example 1 under conditions where the area of ​​the cylindrical segments is perpendicular to the direction of the force applied to the tablet shape.

[0057] The present invention is further illustrated by the following set of embodiments and combinations of embodiments, which are derived from the indicated dependencies and back references. In particular, it should be noted that in each instance where a range of embodiments is mentioned in conjunction with a term such as "the method according to any one of embodiments 1 to 4," it means that all embodiments within this range are expressly disclosed to those skilled in the art, i.e., the wording of this term should be understood by those skilled in the art to be equivalent to "the method according to any one of embodiments 1, 2, 3 and 4." Furthermore, it should be expressly noted that the following set of embodiments represents a preferred constructed part of this specification, which is directed to the general and preferred aspects of the present invention, rather than a set of claims defining the scope of protection.

[0058] 1. A method for reforming ammonia, comprising: (i) providing a reactor containing a catalyst comprising a metal M1 selected from the group consisting of Ni, Co, or Ni and Co; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into the reactor prepared in (i) and contacting the feed gas stream with the catalyst, the contacting being at a pressure of 1 to 50 bara and a temperature of 400 to 1,100° C.; (iv) withdrawing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2. The method includes: 2. The method according to embodiment 1, wherein the contacting is carried out at a pressure in the range of 5 to 50 bara, preferably 10 to 50 bara, more preferably 15 to 45 bara, preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 28 bara, more preferably 20 to 25 bara. 3. The method according to embodiment 1 or 2, wherein the contacting is carried out at a temperature in the range of 450 to 1,000°C, preferably 475 to 975°C, more preferably 500 to 900°C, more preferably 550 to 800°C, more preferably 600 to 750°C, more preferably 650 to 700°C. 4. The method according to any one of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 1-100% by volume of NH3, preferably 3-99.99% by volume, more preferably 5-99.95% by volume, more preferably 10-99.9% by volume, more preferably 12-99.9% by volume, more preferably 20-99.8% by volume, more preferably 22-99.8% by volume, more preferably 30-99.7% by volume, more preferably 40-99.6% by volume, more preferably 50-99.5% by volume. 5. The method according to any one of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 0-50 vol.%, more preferably 0.01-30 vol.%, more preferably 0.02-25 vol.%, more preferably 0.03-15 vol.%, more preferably 0.04-10 vol.%, more preferably 0.05-5 vol.%, more preferably 0.1-1 vol.%, more preferably 0.12-0.5 vol.%, more preferably 0.14-0.16 vol.% N2. 6. The method according to any one of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 0-75% by volume H, preferably 0-60% by volume, more preferably 0-50% by volume, more preferably 0-40% by volume, more preferably 0-35% by volume, more preferably 0-30% by volume H. 7. The method of any one of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 200-20,000 ppmv, preferably 500-15,000 ppmv, more preferably 800-10,000 ppmv, more preferably 1,000-5,000 ppmv HO. 8. The method according to any one of the preceding embodiments, wherein the combined amount of NH3, N2, and H2 in the feed gas stream prepared in (ii) is in the range of 90-100% by weight, preferably 95-99.95% by volume, more preferably 98-99.9% by volume, more preferably 99-99.85% by volume, more preferably 99.7-99.8% by volume. 9. The method according to any one of the preceding claims, which is a process for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and the effluent gas stream withdrawn in (iv) further comprises CO. 10. The method of embodiment 9, wherein the feed gas stream prepared in (ii) further comprises CO2 and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5% or less by volume of HO, more preferably 3% or less by volume, more preferably 1% or less by volume, more preferably 0.5% or less by volume, more preferably 0.1% or less by volume, more preferably 0.05% or less by volume, more preferably 0.01% or less by volume of HO. 11. The method of embodiment 9, wherein the feed gas stream prepared in (ii) further comprises HO and one or more hydrocarbons, and wherein the feed gas stream comprises 5% CO by volume or less, more preferably 3% CO by volume or less, more preferably 1% CO by volume or less, more preferably 0.5% CO by volume or less, more preferably 0.1% CO by volume or less, more preferably 0.05% CO by volume or less, more preferably 0.01% CO by volume or less. 12. The method of embodiment 9, wherein the feed gas stream prepared in (ii) further comprises CO2, H2O, and one or more hydrocarbons. 13. The method of any one of embodiments 9 to 12, wherein the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, preferably C1 to C10 alkanes and mixtures thereof, more preferably C3 to C9 alkanes and mixtures thereof, more preferably C4 to C8 alkanes and mixtures thereof, more preferably C5 to C7 alkanes and mixtures thereof, more preferably C6 alkanes and mixtures thereof. 14. The method of any one of embodiments 9 to 13, wherein the contacting is carried out at a pressure in the range of 10 to 50 bara, preferably 12 to 45 bara, more preferably 15 to 40 bara, more preferably 18 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 30 bara. 15. The method according to any one of embodiments 9 to 14, wherein the feed gas stream prepared in (ii) comprises 0.1 to 75 vol.%, preferably 0.3 to 60 vol.%, more preferably 0.5 to 50 vol.%, more preferably 0.8 to 40 vol.%, more preferably 1 to 30 vol.%, more preferably 12 to 25 vol.% NH3. 16. The method according to any one of embodiments 9 to 15, wherein the feed gas stream prepared in (ii) comprises 10 to 70% by volume, preferably 12 to 60% by volume, more preferably 15 to 50% by volume, more preferably 20 to 40% by volume, more preferably 22 to 29% by volume of one or more hydrocarbons. 17. The method according to any one of embodiments 9 to 16, wherein the feed gas stream prepared in (ii) comprises 0 to 75% by volume HO, more preferably 0.5 to 70% by volume, more preferably 1 to 68% by volume, more preferably 3 to 66% by volume, more preferably 5 to 64% by volume, more preferably 8 to 62% by volume, more preferably 10 to 60% by volume, more preferably 25 to 50% by volume, more preferably 33 to 44% by volume. 18. The method according to any one of embodiments 9 to 17, wherein the feed gas stream prepared in (ii) comprises 0 to 60% by volume CO2, preferably 1 to 58% by volume, more preferably 3 to 56% by volume, more preferably 5 to 54% by volume, more preferably 8 to 52% by volume, more preferably 10 to 50% by volume, more preferably 12 to 20% by volume. 19. The method of any one of embodiments 9 to 18, wherein the feed stream exhibits a HO:C molar ratio, HO to carbon contained in one or more hydrocarbons, in the range of 0 to 4, preferably 0.1 to 3, more preferably 0.1 to 3, more preferably 0.3 to 2.5, more preferably 0.4 to 2, more preferably 0.5 to 1.6. 20. The method of embodiment 19, wherein the catalyst comprises Ni and the feed stream exhibits a HO:C molar ratio of HO to carbon contained in one or more hydrocarbons in the range of 0.6 to 3, more preferably 0.7 to 2.5, more preferably 0.8 to 2, more preferably 0.9 to 1.6. 21. The method of embodiment 19 or 20, wherein the catalyst comprises Co and the feed stream exhibits a HO:C molar ratio, HO to carbon contained in one or more hydrocarbons, in the range of 0.2 to 2.5, preferably 0.3 to 2, more preferably 0.4 to 1.8, more preferably 0.5 to 1.5. 22. The method of any one of embodiments 9 to 21, wherein the feed stream exhibits a CO2:C molar ratio, CO2 to carbon contained in one or more hydrocarbons, in the range of 0 to 4, preferably 0.1 to 3, more preferably 0.2 to 2, more preferably 0.3 to 1.5, more preferably 0.4 to 0.8. 23. The method of any one of embodiments 9 to 22, wherein the feed stream exhibits an NH3:C molar ratio, NH3 to carbon contained in one or more hydrocarbons, in the range of 0 to 5, preferably 0 to 4, more preferably 0.001 to 3, more preferably 0.005 to 2, more preferably 0.01 to 1. 24. The supply stream is 500 to 16,000 h -1 , preferably 700 to 14,000h -1 , more preferably 800 to 12,000 h -1 , more preferably 900 to 10,000 hours -1 , more preferably 950 to 8,500 hours -1 , more preferably 1,000 to 8,000 hours -1 24. The method of any one of the preceding embodiments, wherein the gas is fed to the reactor at a gas hourly space velocity in the range of 25. The method of any one of embodiments 9 to 24, wherein the effluent gas stream withdrawn in (iv) further comprises CO2. 26. The effluent gas stream withdrawn in (iv) exhibits a stoichiometric coefficient R in the range of 0.1 to 3, wherein R is a gas having a stoichiometric coefficient R of formula (I):

number

[0059] [Figure 1]Figure 1 shows the results of NH3 reforming from Example 4 using the Ni-based catalyst of Example 1 at 30 bar and GHSV of 8000 h-1 with 5000 ppmv HO in the NH3 feed stream. In this figure, ammonia conversion (%) is plotted along the vertical axis and temperature (°C) is plotted along the horizontal axis. The measured conversion is shown as a medium grey circle and the equilibrium conversion at that temperature is shown as a dark grey square. [Diagram 2] Figure 1 shows the results of NH3 reforming from Example 4 using the Co-based catalyst of Example 2 at 30 bar and GHSV of 8000 h-1 with 5000 ppmv HO in the NH3 feed stream. In this figure, ammonia conversion (%) is plotted along the vertical axis and temperature (°C) is plotted along the horizontal axis. The measured conversion is shown as a medium grey circle and the equilibrium conversion at that temperature is shown as a dark grey square. [Diagram 3] 2 shows the results of NH3 reforming from Example 4 using a Ni-based catalyst with PGM and transition metal promoters at a GHSV of 2000-1, 30 bar, and 10,000 ppmv H2O in the NH3 feed stream. [Figure 4] On the left is a side view of the arrangement for determining lateral crush strength 1 (SCS1), in the middle a side view of the arrangement for determining lateral crush strength 2 (SCS2), and on the right a side view of the arrangement for determining lateral crush strength 3 (SCS3).

[0060] The present invention is further illustrated by the following examples. EXAMPLES

[0061] Reference Example 1: Determination of Side Crush Strength The lateral crushing strength was determined with a semi-automatic tablet testing system SotaxST-50WTDH. The lateral crushing strength was measured at a constant speed of 0.05 mm / s. It is possible to test in the range of 0-800 N. For each measurement, the orientation of the sample was adjusted on a horizontal rotating table, with fine adjustments made manually. In addition, some measurement parameters were adjusted, if applicable, depending on the orientation and properties of the sample, such as mass, height / thickness, diameter, and breaking strength. The obtained data were evaluated with the scientific program q-doc prolab (version 4fsp2(4.10)). Tablet geometries with a 4-hole cross section were tested, whereby three mutually perpendicular positions were examined to determine lateral crushing strength 1, lateral crushing strength 2, and lateral crushing strength 3. The relative standard deviation of crushing strengths 1, 2, and 3 was 7.48%.

[0062] As can be seen from Figure 1, side crush strength 1 refers to the position of the tablet shape in the semi-automatic tablet testing system where the sample stands on the rotating table with two cylindrical segments sandwiched between the longitudinal grooves, side crush strength 2 refers to the position where the sample stands on the rotating table with one cylindrical segment, and side crush strength 3 refers to the position where the hole is parallel to the direction of the force applied to the sample during the test.

[0063] Reference Example 2: Determination of lateral crush strength The side crushing strength was determined with a tablet testing system (TypBZ2.5 / TS1S, Zwick). The side crushing strength was measured using a punch tool. The side crushing strength was recorded as soon as the sample was broken. For each measurement, the orientation of the sample was manually adjusted on a horizontal table. The punch tool was positioned to punch from above. Furthermore, some measurement parameters were adjusted, if applicable, depending on the orientation and properties of the sample, such as mass, height / thickness, diameter, and breaking strength. Tablet geometries with a 4-hole cross section were tested, whereby three mutually perpendicular positions were examined to determine side crushing strength 1, side crushing strength 2, and side crushing strength 3. As can be seen from Figure 1, side crush strength 1 refers to the position of the tablet shape in the semi-automatic tablet testing system where the sample stands on the rotating table with two cylindrical segments sandwiched between the longitudinal grooves, side crush strength 2 refers to the position where the sample stands on the rotating table with one cylindrical segment, and side crush strength 3 refers to the position where the hole is parallel to the direction of the force applied to the sample during the test.

[0064] Example 1: Preparation of Ni-containing catalyst The Ni-containing catalyst was prepared according to the method described in Example E1 of WO 2013 / 068905 A1.

[0065] An aqueous nickel nitrate solution (14% Ni concentration) was used instead of ground nickel nitrate hexahydrate. The various components were mixed into a paste which was then extruded. The extrudate was ground, dried and calcined at low temperature before being sieved to a target particle size fraction of 200-900 μm.

[0066] The sieved powder was then mixed with 2.8% by weight of graphite (Asbury Graphite 3160) and 5.5% by weight of cellulose (Arbocel BWW40). The resulting mixture was tableted into a compact having a four-hole cross section as shown in FIG. 1 of WO 2020 / 157202A. For sintering, the compact was heated to a temperature of 1,030 to 1,050 ° C in an annealing furnace and held for 4 hours.

[0067] The sintered compact had a nickel content of 15.5 wt %, a magnesium content of 14.0 wt %, and an aluminum content of 29.5 wt %.

[0068] Example 2: Preparation of Co-containing catalyst The Co-containing catalyst was prepared according to Example 1 of WO 2020 / 157202 A1.

[0069] Example 3: Preparation of Ni-based catalysts containing PGM or transition metal promoters Catalysts containing Ni and platinum group metal or transition metal promoters were prepared according to the method described in Example E1 of WO 2013 / 068905 A1. A part of the Ni salt was replaced with an Fe salt (here Fe(NO3)3(H2O)9, substitution degree based on Ni content 40 at.%). Alternatively, a part of the Ni salt (here Ni nitrate) was replaced with a Ru salt (here Ru(NO)(NO3)3 solution, Ru concentration 19.7%, substitution degree based on Ni content 5 at.%). The respective metal salt mixtures were mixed with hydrotalcite and an appropriate amount of water to prepare an extrudable paste. This paste was extruded in the next step. Subsequent heat treatment of the obtained extrudates was the same as in Example 1 (WO 2013 / 068905 A1 Example E1).

[0070] This procedure yielded Ni+Fe and Ni+Ru supported catalysts, respectively.

[0071] Example 4: Catalyst testing in NH3 reforming under high pressure The catalysts obtained according to examples 1-3 were reduced in inert gas (Ar or N2) mixtures with increasing concentration of H2 from 5 to 50 vol.% (with increasing temperature) at temperatures between 450 and 650 °C for Ni catalysts and 450 and 850 °C for Co catalysts. The catalytic NH3 reforming tests were carried out under p(NH3) of 30 bar. H2O was added to the NH3 feed stream in proportions of 5000 to 10,000 ppmv. Furthermore, the catalysts were subjected to 2,000 and 8,000 h -1The conversion of NH3 at the corresponding GHSV at 30 bar as a function of temperature is shown in Table 1. In addition, an 8,000 h -1 The results of the samples of Examples 1 and 2 at GHSV of 10,000 ppmv are shown in Figures 1 and 2, and the results of the samples of Examples 1 and 2 at GHSV of 10,000 ppmv H2O at 2,000 ppmv H2O are shown in Figures 1 and 2. -1 The results of the samples of Examples 1 and 3 in GHSV are shown in FIG.

[0072] [Table 1]

[0073] As can be seen from the catalyst test results shown in Table 1 and Figure 1, the ammonia reforming reaction performed using the Ni catalyst of Example 1 achieves increasing conversion with increasing temperature, with the conversion nearly reaching the equilibrium conversion for that temperature at 650°C. Figure 2 shows the results obtained from ammonia reforming using the Co catalyst of Example 2. Although the conversion at 650°C is not as high as that obtained using the Ni catalyst shown in Figure 1, a similar increased conversion with increasing temperature is obtained.

[0074] Finally, the results of catalytic testing of the Ni catalysts of Examples 1 and 3 at lower GHSV and higher amounts of steam are shown in Figure 3. As can be seen, under these conditions, the Ni catalyst of Example 1 reaches nearly equilibrium conversion at 650°C. Furthermore, when promoted with Ru or Fe, the ammonia conversion increases more rapidly, with the conversion for the promoted catalyst reaching nearly equilibrium conversion already at 600°C and achieving more than 98% conversion at 650°C.

[0075] Example 5: Simulation of hybrid reforming of NH3 with hydrocarbons with or without CO2 Due to the high activity of the catalyst at the corresponding conditions (20 bar, high temperature), the catalytic performance at equilibrium conditions is expected if the residence time is appropriately selected. To investigate this, simulations were performed using the software Aspen Plus V11. Tables 2 and 3 show the inlet and outlet concentrations of NH3 under dry conditions and for example the mixed reforming of hydrocarbons (here CH4) / CO2. As can be seen from the results in Tables 2 and 3, gradually increasing the NH3 as a co-feed stream increases the R value due to the additional H2 formed by NH3 reforming.

[0076] [Table 2]

[0077] [Table 3]

[0078] The simulation results shown in Tables 2 and 3 illustrate the concept of the hybrid reforming approach (NH3+HC+CO2+H2O) in manipulating and controlling the R-value of the final syngas composition. The increase in R-value is expected to start from 0.1 (from hybrid reforming with very dry reforming conditions, little H2O, and lots of CO2 / HC) and reach R-values ​​of 1-1.5 for Fischer-Tropsch-like reactions or one-stage DME, for example. However, syngas with R-values ​​above 2 are also possible.

[0079] The same applies to the combined reforming of NH3 and HC / CO2 under dry conditions, starting from an R value of 0.5 and potentially eventually reaching R>2 with increasing NH3 amount. Thus, essentially all R values ​​between 0.1 and 2.5 may be adjusted by the amount of NH3 co-fed to the HC / CO2 / H2O gas mixture.

[0080] Example 6: Catalysis Testing The catalytic tests were carried out in a single reactor test unit. This unit allowed for a wide range of test conditions in temperature and pressure up to 1100 °C and 20 bar (gauge). Carbon dioxide (denoted CO2-in), methane (denoted CH4-in), nitrogen (denoted N2-in), ammonia (denoted NH3-in), and argon (denoted Ar-in) were supplied as gas feed streams and controlled online by mass flow controllers (MFCs). Water (denoted H2O-in) was added as vapor to the feed stream by an evaporator connected to a water reservoir. Analysis of the product gas composition was performed by online gas chromatography using argon as an internal standard. Gas chromatography analysis allowed the quantification of hydrogen, carbon monoxide, carbon dioxide, methane, ammonia, nitrogen, and C2 components. For catalytic tests, the catalyst material was divided (0.5-1.0 mm) and then 15 ml of the aliquot was tested as catalyst. As catalyst, a mixed metal oxide comprising Ni and Mg according to Example E1 of WO 2013 / 068905 A1 was used. The sample was placed in the thermostatic area of ​​the reactor using a ceramic utensil. The temperature shown represents the oven temperature.

[0081] The results of the catalytic tests are shown in the table below. Phase 1+2 and Phase 3+4 show different types of biogas without and with NH3 co-feeding for R-value adjustment respectively.

[0082] [Table 4]

[0083] As can be seen from the results shown in Table 4, the process according to the invention, in which catalysts containing Ni and / or Co are used, allows the reforming of ammonia to provide a synthesis gas stream, especially in a combined reforming approach with NH3 and hydrocarbons, and in particular to produce synthesis gas with R values ​​that match those of the corresponding downstream applications (e.g. MeOH production, DME production, or Fischer-Tropsch processes).

[0084] Cited prior art documents: ·International Publication No. 2013 / 068905A Brochure ·International Publication No. 2013 / 118078A Brochure ·International Publication No. 2020 / 157202A1 Brochure ·Int.J.of Hydr.and Energ.,2020,45,8965-8974 ·Int.J.of Hydr.and Energ.,2014,39,35,19990-19999 Top Catal(2016)59:1438-1457 ·International Publication No. 2021 / 175785A1 Brochure ·Catal.Sci.Technol.,2020,10,5027-5035

Claims

1. 1. A method for reforming ammonia, comprising: (i) providing a reactor containing a catalyst comprising a metal M1 selected from the group consisting of Ni, Co, or Ni and Co; (ii) NH ３ preparing a feed gas stream comprising: (iii) feeding the feed gas stream prepared in (ii) into the reactor prepared in (i) and contacting the feed gas stream with the catalyst, wherein the contacting is carried out at a pressure of 1 to 50 bara and a temperature of 400 to 1,100°C; (iv) withdrawing an effluent gas stream from the reactor, wherein the effluent gas stream is H ２ and N ２ and steps including A method comprising:

2. (ii) the feed gas stream prepared in step (ii) contains 200 to 20,000 ppmv H ２ The method of claim 1 , comprising:

3. (ii) the NH contained in the feed gas stream prepared in ３ , N ２ , and H ２ The method according to claim 1, wherein the total amount of is in the range of 90 to 100% by weight.

4. 1. A process for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) comprises one or more hydrocarbons and CO ２ and H ２ and one or more of O, and the effluent gas stream withdrawn in (iv) further comprises CO.

5. (ii) the feed gas stream prepared in (ii) is ２ , H ２ 5. The method of claim 4, further comprising: O; and one or more hydrocarbons.

6. 5. The method of claim 4, wherein the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof.

7. 5. The process of claim 4, wherein the contacting is carried out at a pressure in the range of 10 to 50 bara.

8. (ii) the feed gas stream prepared in step (ii) is 0.1 to 75% by volume of NH ３ The method of claim 4, comprising:

9. 5. The method of claim 4, wherein the feed gas stream prepared in (ii) comprises 10 to 70% by volume of one or more hydrocarbons.

10. The supply flow is 500 to 16,000 h －１ 10. The process of claim 1, wherein the gas is fed to the reactor at a gas hourly space velocity in the range of

11. The effluent gas stream withdrawn in (iv) exhibits a stoichiometric coefficient R in the range of 0.1 to 3, wherein R is a gas having a stoichiometric coefficient R of formula (I): [Equation 1] (where c(H ２ ), c(CO ２ ), and c(CO) are the H in the effluent gas stream, respectively. ２ , CO ２ , and the molar concentration of CO The method of claim 4, defined according to

12. The method of claim 11, wherein the stoichiometric coefficient R is in the range of 0.5 to 3.

13. 10. The method of claim 1, wherein the catalyst contained in the reactor provided in (i) further comprises Al and O.

14. 14. The method of claim 13, wherein the catalyst contained in the reactor provided in (i) comprises Ni as the metal M1, and the catalyst further comprises Mg.

15. 14. The method of claim 13, wherein the catalyst contained in the reactor provided in (i) comprises Co as the metal M1, and the catalyst further comprises La.

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